Amide-nickel salt complexes

ABSTRACT

AMIDE-NICKEL SALT COMPLEXES HAVING CONSTITUENTS OF SUBSTITUTED 2-AMINOMALONAMIDES AND NICKEL SALTS ARE PRODUCED, WHICH COMPLEXES ARE USEFUL AS A CATALYST IN THE OLIGOMERIZATION OF MONOOLEFINS. BIS(N,N&#39;&#39;-DICYCLOHEXYL2 - (CYCLOHEXYLAMINO)MALONAMIDE) REACTS WITH NICKEL CHLORIDE TO FORM BIS(N,N&#39;&#39; - DICYCLOHEXYL - 2 - (CYCLOHEXYLAMINO)MALONAMIDE)DICHLORONONICKEL, WHICH IS USED AS AN OLIGOMERIZATION CATALYST FOR PROPYLENE.

United States Patent Int. Cl.-C07f.75/.04; C07c3/10 US. Cl. 260-439 R I2 Claims ABSTRACT OF THE DISCLOSURE Amide-nickel salt complexes havingconstituents of substituted Z-aminomalonarnides and nickel salts areproduced, which complexes are useful as a catalyst in theoligomerization of monoolefins. Bis[N,N'-dicyclohexyl- 2(cyclohexylamino)malonamide] reacts with nickel chloride to formbis[N,N' dicyclohexyl 2 (cyclohexylamino)malonamide]dichloronickel,which is used as an oligomerization catalyst for propylene.

BACKGROUND O THE INVENTION I This invention relates to the production ofnovel amidenickel salt complexes. In another aspect, this inventionrelates to a process for production of amide complexes of nickel saltsfrom 2-aminomalonamides. In still another aspect, this invention relatesto catalysis of oligomerization reactions of monoolefins.

V A copending application, Ser. No. 795,676 presents a method ofproducing the. novel substituted 2-aminomalonamides of which the presentnovel amide-nickel complexes are derivatives. This, method entailsreacting a suitable monoolefin with hydrogen cyanide and anhydroushydrogen fluoride for a period of time suflicient to form a reactionproduct of these reactants. Suitable olefins for the reaction have theformula RCH=CHR wherein the total number of carbon atoms in the olefinmolecule is in the range of 2 to about 30 carbon atoms and wherein R isselected from hydrogen and alkyl, cycloalkyl, and aryl radicals, andcombinations thereof. The

reaction mixture is then hydrol ized with suflicient water to form asubstituted 2-aminomalonamide.

Although nickel containing salts have been used as .catalyst for olefinoligomerization, prior to this invention a complex of a nickel salt anda. substituted 2-aminomalonamide has been unknown for such use.

Accordingly, an object of this invention is to provide novelamide-nickel salt complexes.

Another object of this invention is to provide a suitable catalyst formonoolefin oligomerization.

Other aspects, objects, and the several advantages of this inventionwill be apparent to those skilled in the art from a study of thisdisclosure.

jSUMMARY OF THE INVENTION In another embodiment of the invention theamidenickel salt complex produced above is a suitable catalyst forolefin oligomerization. The amide-nickel salt complex can be contactedwith an organoaluminum compound I and an olefin or mixture of olefins ata temperature for a time sulficient to oligomerize the olefins present.

3,651,111 Patented Mar. 21, 1972 A process for preparing the substituted2-aminomalonamides which is suitable for the preparation of thenovelnickel complex of the present invention is described in a copendingapplication, Ser. No. 795,676. The compounds suitable for the presentinveutioncan be represented by the formula CONHCHRGHzR I HNHGHRCH RoNHenncmR wherein each R is selected from hydrogen and alkyl,cycloalkyl, and aryl radicals, and combinations thereof such as alkarylradicals, aralkyl radicals, and the like with the further proviso thattwo R groups together, on adjacent carbon atoms, can represent adivalent radical selected from alkylene, cycloalkylene, cycloalkylandaryl-substituted alkylene, and alkyl-, cycloalkyl-, and arylsubstitutedcycloalkylene. In a presently preferred embodiment the total number ofcarbon atoms in the malonarnide does not exceed about 93 carbon atoms.

Some examples of suit-able substituted 2-amin0malonamides are and thelike mixtures thereof.

Any convenient nickel (II) salt can be used for preparing the novelnickel complex of the present invention. Preferred nickel salts are thenickel halides, the nickel pseudo halides, or the nickel salts ofinorganic or organic acids. Some examples of suitable nickel salts areNiCl NiCl -6H O, NiBr NiI NiF Ni(CN) Ni(SCN) Ni(OCN) Ni(acetate)z,Ni(benzoate) Ni(NO NiSO and the like, and mixtures thereof.

The novel nickel complex of the present invention is prepared bycombining the suitable nickel salt and the suitable substitutedZ-aminomalonamide under conditions of time and temperature which aresuflicient to permit the complex to be formed. In such a preparation,the molar proportion of the substituted 2-aminomalonamide to the nickelsalt will be approximately 2:1 although other proportions in the rangeof from about 0.5 :1 to about 5:1 can be used but at the obvious expenseof economy. The contact of these two ingredients will generally be madeat a temperature in the range of about 25 to about 0., preferably 0 toabout 60 C., for a time in the range of from a few seconds up to about24 hours, preferably in the presence of a diluent in which theingredients of the reaction are at least partially soluble. Forpreparing the amide-nickel salt complex alcoholic solvents are generallypreferred because of their availability. Lower mono-hydroxy alcoholssuch as methanol, ethanol, isopropanol, and the like, canbe used.

Examples of novel nickel complexes produced invention are:

bis[N,N'-diethyl-2-(ethylamino)malonamide]dichloronickel,

bis [N,N'-diisopropyl-2-(isopropylamino)malonamide] dibromonickel,

by this *bis{'N;N'-di-sec-butym='(sec-butylamino)malonanfide]"*"' These'novernickel complexes can be represented'by the dicyanonickel, ("'g?formula: bis [N,N' -bis l ethylbutyl)'}2- l-methylbutylamino) h CONHdHRCHQR 'malonamide]dichloronickel, 1 7bi's[N,N'-bis(1-ethylpropyl)-2-(l-ethylpropylamino) B:|malonamide]diacetatonickel, I p I CH C z p i SImNffl y Y 1- i Y Q Y mwherein eachR is selected from hydrogen and alkyl, cycloalkyl, and arylradicals,'and'combinations-thereof.-sucIi as Y P Y!)- y p y alkarylradicals,aralkyl radicals, and thelike withthemalonamide]dibenaoatomckel, 0 further proviso that two R groupstogether,'o'n adjacent Y!Ql/ t y y carbon atoms, can, represent adivalent radical selected malollaflpdeldlthlmyanatomckels from alkylene,cycloalkylene, cycloalkyland aryl-substihy n y y y tuted alkylene, andalkyl-, cycloalkyl, and aiyl-substituted amll10)1!1a1011am1de]dlchlomnlckcl, cycloalkylene; and wherein X is anelement orradical that y 15 will combine with nickel toform a nickel salt.ma10I1afl1de]Sulfatofllckel, The amide-nickel salt complex thus-producedcan be hy p f yny p y used in the preparation of a catalyst which willpromote ammomjlalonamldelflltl'atomckels the oligomerization ofmonoolefins. The catalyst is pre- 9 y e y y y pared by the combinationof a suitable organoaluminum 0 compound with the novel nickelcomplexunder condihy q Y y tions of time and temperature which permitthe catalytiammohg m ifl cally active reaction product to form. Thiscombination [N -Q y yl yn-Q-( Y Y occurs very readily and, ingeneral,these components can butylamino)malonamide] dichloronlck be mixed at anyconvenient temperature within the range Y P PY Y y of -80 to about 100C. for a few seconds 'or for periodslsopfopylhexylamlno)malonamldeldibmmflnickel, of up to several hours inthe presence of a diluent invwhich -P PY Y P Y -P PY both the componentsareat least partially soluble. .Anytert-butylheptylamino)malonamide]dichloronickel, convenient diluent suchas benzene, heptane, cyc'lohexane,bis[N,N'-bis(1-methyl-3-cyclohexylpropyl)-2-( l-methylchlorobenzene,methylene chloride,ethylene chloridep and3-cyclohexylpropylamino)malonamide]dibromonickel, the like can be e r spl p s Halogenatd .d bi N,N'.bi 1- h 1-3-(2. th 1 1 t 1)b t 1]-2- entsare frequently preferred. The mixing of the two cata- [baby].3-(2methy1cyc1penty1)butylamino] lyst components is generally carried out'in the substantial malonamide]dipropionatonickel, absence of air ormoisture, generally in an inert atmosbis[NNr bis(a methylbenzyl) z (amethylbenzylamino) phere. After the catalytic species is formed, it neednot be isolated but may be added directly ,to the olefin oligomerizationzone as a solution in its preparation solvent. If desired, the catalystcomponents can be separately added, in any order, to the reaction zoneeither in the presence malonamide] diiodonickel, bis [N,N'-bis1-benzylbutyl)-2- l-benzylbutylamino) malonamide1dibromonickel,

his P U' i or absence of the feed olefin. However, it has been found ppylhq y l o l q z 40 that catalysts of greater acti vity'a're' obtainedwhen the 3 'dlfyclobutyl'z'(cyclobutylammo)malonamlde] nickel complex iscontacted first with the olefin and then dlmtmto elt with theorganoaluminum compound. Ihis[N,N'-d1cyclopentyl-2-(cyclopentylammo)malon- The l fi which can beoligomerized (generally to amideloXalatoflickeL dimers) by the novelcatalyst system of the present inveny y =Y y tion include both acrylicand cylic olefins having up to sulfatonickel, about 12 carbon atoms permolecule. These can 'bebis[N,N-bis(3-methylcyclooctyl)-2-(3-methylcyclobranched or unbranched,terminal or internal, but any octylamino)malonamide1dichloronickel,branching is preferably at least one carbon atom removedbis[N,N'.dicyc1od0decy1.2-(cyclododecylamino) from the double bond.-Somespecific examples of'these are ethylene, propylene, butene-l, butene-Z,pentene-l, pentene-2, cyclopentene, cyclohexene, 3-methylbutene-1,cycloheptene, hexene-Z, heptene-l, cyclooctene; 4,4-dimethylheptene-2,decene-l, dodecene-l, and the like, and mixtures thereof. Terminalacyclic olefins having up to m'alonamide1diiodonickel,bis[N,N'-dicyclooctadecyl-2-(cyclooctadecylamino) malonamide]dithiocyanatonickel, .bis [N,N'-bis(4-phenylcyclohexyl)-2-(4-phenylcyclohexylamino)malonamide]dichloronickel, about 6 carbon atomsare u e presen y preferred and particublslNNhms'fzyclopemylcygooclyl)'2'(S'CYCIOPemYI' larly effective results areobtained with ethylene, andprocyclooctylammo)malonamide]dlbenzoatomckel, pylene. D f Theorganoaluminum compounds suitable for use in v amide ]d iluoroniclrel,preparing the novel catalyst system of the present invenb tion areselected from those having the formulas; CRgAl,norbornylamino)malonamide]dibutyratonickel, RzAlx, or RAlXz, Thcompounds, lw ll kn w -i '-b -P Y l/ -P nylrthe art and can be preparedby conventional methods. bornylamino)malonamide]dichloronickel, 1 Somespecific examples of these are methylaluminumdibis[N,N-bis(1-cyc1ohexyl-2-norbornyl)-2-(l-cyclohexylchloride,dimethylaluminum chloride, diethylaluminumZ-norbor'nyIamino)malonamide]difluoronickel, bromide, vinylaluminumdiiodide, tributylaluminum,-d ig qm n fl1-m y1 1 -2- l o i butylaluminumchloride, phenylaluminumdibromide, di-

m dha jd ddn k benzylaluminum chloride, 4-t olylalumin um dichloride, biN bi 1 e thy1propy1) 2 (LmethYlblitSdamino) dodecylalummum dlbromlde,eicosylalummum difluoride,

' 'm l n l idfldibf m j k L' I .and the like, and mixtures thereofsuchasmethylalurnibis[N (l methylbutyl) Nt (bahylpropyl) 2 (1 methyl 1mm sesquichlonde and ethylaluminum sesquichlonde.butylamifio)malonamide]dichloronickel, P F pfefmed alummum' cmpundsbis[N-(l-methylbutyl)-N'-(l-ethylpropY1)-2-(l-ethyl- "3 g fgf the alkylhydrocarbons h as .me ane e propylammmmalonamlde]dlchloromckel Anorganoaluminum compound and the complex nickel and the like. 7 5compound are generally utilized, for use in this invention,

in proportions in the range of from about 0.5 :1 to about 30:1 moles ofthe aluminum compound per mole of the nickel complex. Still greaterquantities of the aluminum component are sometimes desirable to scavengecatalyst poisons which may be in the system.

The Oligomerization of the olefin or mixture of olefins can take placeat any convenient temperature within the broad range of about 80 toabout 200 C., preferably 10 to about 50 C. The reaction can be carriedout at any convenient pressure which is sufficient to keep at least someolefin feed dissolved in the reaction medium. Thus, the reaction iscarried out in the liquid phase and pressures in the range of from aboutto about 2000 p.s.i.g. can be used. The reaction can be carried outeither in the presence or absence of a diluent, preferably in thepresence of a diluent, and diluents such as those described for thecatalyst preparation can be used. The time of contact will depend uponthe degree of conversion but will, generally, be in the range of fromabout 0.1 minute to 20 hours, preferably 5-120 minutes. The proportionof catalyst composition to olefin feed in the reaction zone willgenerally be in the range of from about 0.001-100 millimoles of nickelcomplex for each mole of olefin feed.

Any conventional contacting technique can be utilized for the olefinOligomerization, and batchwise or continuous operation can be utilized.After the reaction period, the products can be separated and/or isolatedby conventional means such as by fractionation, crystallization,adsorption, and the like. If desired, the catalyst can be destroyed bytreatment with Water prior to the separation of products.

The process will generally produce substantial quantities of olefinicdimers. However, other higher oligomers such as trimers, tetramers, andthe like can also be present in varying degrees depending upon theolefin.

Below are presented illustrative examples of a typical preparation of anamide-nickel salt complex of this invention and the use of this complexin catalyzing the oligomerization of a monoolefin.

EXAMPLE I Preparation of bis [N,N'-dicyclohexyl-2- cyclohexylaminomalonamide] dichloronickel To a 7 ounce glass reactor, equipped with amagnetic stirrer, were added 1.19 g. (5 mmoles) of NiCl -6H O' and 10ml. of absolute ethanol. The mixture was stirred at room temperature todissolve the nickel salt.

To another stirrer equipped flask were added 1.82 g. (5 mmoles) of his[N,N'-dicyclohexyl-2-(cyclohexylamino)malonamide] and 10 ml. of absoluteethanol. The mixture was stirred and warmed to dissolve the solid.-

The nickel solution was added to the amide solution. On stirring andcooling, a fine baby-blue precipitate separated. It was then warmed toredissolve the solid, and the stirring was stopped and the solutionallowed to stand over night at room temperature to allow the crystals toform undisturbed. Well-formed baby-blue crystals were the result. Thesewere filtered and dried under vacuum in a desiccator at room temperatureover anhydrous calcium sulfate yielding 1.47 g. of the novel nickelcomplex bis [N, N dicyclohexyl 2(cyclohexylamino)malonamide]dichloronickel.

An elemental analysis of the novel complex, calculated as (C H N 0 NiClwas carried out with the following results:

The novel complex was stable in that it did not change when heated up to250 C.

EXAMPLE II Oligomerization of propylene usingbis[N,N-dicyclohexyl-2-(cyclohexylamino)malonamide]dichloronickel as acatalyst To a dry 7 ounce glass reaction flask, fitted with a magneticstirrer, were added 20 ml. of chlorobenzene and 0.0493 g. (0.1 mmole) ofbis[N,N-dicyclohexyl-2-(cyclohexylamino malonamide] dichloronickel.Propylene was pressured in at 30 p.s.i.g. to saturate the solvent. Thepressure was then reduced to 5 p.s.i.g. and 1.5 ml. of a 1 molarethylaluminum dichloride solution in chlorobenzene was added. Thepropylene pressure was again increased to 30 p.s.i.g. and propylene wasslowly absorbed by the reaction mixture. After 10 minutes, an additional1.5 ml. quantity of the 1 molar solution of ethylaluminum dichloride wasadded. During the next 30 minutes, propylene was absorbed by thereaction mixture very rapidly.

The reaction mixture was then quenched by the addition of 20 m1. ofwater, the organic layer was separated, and 34.4 g. of propylene dimerswere isolated by distillation.

A sample of the dimers was catalytically reduced with hydrogen and thesimplified mixture was analyzed by gas-liquid chromatography to learnthe skeletal distribution of the original propylene dimers. The analysisof the hydrogenated mixture showed, in weight percent, the following:60.50 2-methylpentane, 35.23 n-hexane, 1.87 2,3- dimethylbutane, and2.40 3-methylpentane.

I claim:

1. An amide-nickel salt complex of the formula C ONHCHRCH2R JHNHCHRCH RNiXz ONHCHRCHzR wherein R is selected from the group consisting ofhydrogen and alkyl, cycloalkyl and aryl radicals and combinationsthereof, with the further proviso that two R groups together on adjacentcarbon atoms can represent a divalent radical selected from alkylene,cycloalkylene, cycloalkyl and aryl-substituted alkylene, and alkyl-,cycloalkyl-, and aryl-substituted cycloalkylene; wherein the totalnumber of carbon atoms in the amide portion of the complex does notexceed about 93 carbon atoms per amide moiety; and wherein NiX isselected from the group consisting of nickel halides, nickelpseudohalides, or the nickel salts of organic or inorganic acids.

2. The amide-nickel salt complex of claim 1 wherein the said complex isbis [N,N'-dicyclohexyl-2(cyclohexylamino) malonamide] dichloronickel.

References Cited UNITED STATES PATENTS 2,854,458 9/1958 Reppe et a1.260-326.5

TOBIAS E. LEVOW, Primary Examiner A. P. DEMERS, Assistant Examiner US.Cl. X.R.

'252431 N; 260--429 J, 683.15 D

